2-imino-5-alkylamino-1,3-dithianes

ABSTRACT

THE PRESENT INVENTION CONCERNS NOVEL COMPOUNDS OF THE FORMULA:   2-(Y-N=),5-(R1-N(-R2)-)-1,3-DITHIANE   WHEREIN R, IS ALKYL OF 1 TO 5 CARBON ATOMS, R2 IS HYDROGEN OR ALKYL OF 1 TO 5 CARBON ATOMS AND Y IS HYDROGEN. HYDROXY, ALKYL OF 1 TO 5 CARBON ATOMS, CYCLOALKYL OF 5 OR 6 CARBON ATOMS, CYANO, -COOR3, -COR, WHEREIN R3 IS ALKYL OF 1 TO 5 CARBON ATOMS, ALKENYL OF 2 TO 5 CARBON ATOMS, CYCLOALKYL OF 5 OR 6 CARBON ATOMS, OR FLUORO, CHLORO OR BROMO SUBSTITUTED ALKYL OF 1 TO 5 CARBON ATOMS, ALKENYL OF 2 TO 5 CARBON ATOMS OR CYCLOALKYL OF 5 OR 6 CARBON ATOMS, -OCONHR4 OR -OCONR4R5 WHEREIN R4 IS ALKYL OF 1 TO CARBON ATOMS ARYL OR ARYL SUBSTITUTED BY ALKYL OF 1 TO 5 CARBON ATOMS, FLUORINE, CHLORINE OR BROMINE AND R5 IS HYDROGEN OR ALKYL OF 1 TO 5 CARBON ATOMS. THE COMPOUNDS POSSESS INSECTICIDAL PROPERTIES.

United States Patent Oflice ABSTRACT OF THE DISCLOSURE The present invention concerns novel compounds of the formula:

RI S R2 5 wherein R is alkyl of 1 to 5 carbon atoms, R: is hydrogen or alkyl of 1 to 5 carbon atoms and Y is hydrogen, hydroxy, alkyl of 1 to 5 carbon atoms, cycloalkyl of 5 or 6 carbon atoms, cyano, -COOR -COR wherein R is alkyl of 1 to 5 carbon atoms, alkenyl of 2 to 5 carbon atoms, cycloalkyl of 5 or 6 carbon atoms, or fluoro, chloro or bromo substituted alkyl of 1 to 5 carbon atoms, alkenyl of 2 to 5 carbon atoms or cycloalkyl of 5 or 6 carbon atoms, -OCONHR or OCONR R wherein R is alkyl of 1 to 5 carbon atoms, aryl or aryl substituted by alkyl of 1 to 5 carbon atoms, fluorine, chlorine or bromine and R is hydrogen or alkyl of 1 to 5 carbon atoms.

The compounds possess insecticidal properties.

The present invention relates to heterocyclic compounds and more specifically to 2-imino-1,3-dithiane compounds.

The present invention provides compounds for For mula I,

R] S C R2 8 wherein or -OCONR,R wherein R is alkyl of 1 to 5 carbon atoms, aryl or aryl substituted by alkyl of 1 to 5 carbon atoms, fluorine, chlorine or bromine and R is hydrogen or alkyl of 1 to 5 carbon atoms.

When R R Y, R R and R are alkyl, this may be straight or branched.

The present invention also provides a process for the production of a compound of Formula I, which comprises (a) Reacting a compound of Formula II,

R1 CHaSH N-CH R2 CHzSH (II) wherein R and R are as defined above,

with a compound of Formula III,

Cl--CEN (III) in an inert atmosphere, to obtain a compound of Formula Ia,

R] S I N =NH R2 8 wherein R and R are as defined above,

(b) Reacting a compound of Formula Ia, as defined above with, a compound of Formula XIV,

(XIV) wherein either Y, is hydroxy, alkyl of 1 to 5 carbon atoms or cycloalkyl of 5 or 5 carbon atoms, or

W, is fluorine, chlorine or bromine and Y bis -COOR or COR wherein R is as defined a ove,

to produce a compound of Formula Ic,

s /N =N-Ye R2 S wherein R and R are as defined above and Y is hydroxy, alkyl of 1 to 5 carbon atoms, cycloalkyl of 5 or 6 carbon atoms, COOR or COR wherein R is as defined above, with the proviso that when R of Formula Ia is hydrogen and W of Formula XIV is fluorine, chlorine or bromine, the amino function of the compound of Formula Ia is protected by a protecting group which is split 01f after the reaction with a compound of Formula XIV,

wherein either W is isocyanate and Y, is alkyl of 1 to 5 carbon atoms, aryl or aryl substituted by alkyl of 1 to 5 carbon atoms, fluorine, chlorine or bromine, or

W is fluorine, chlorine or bromine and Y is CONHR or --CONR,R wherein R and R are as defined above,

to produce a compound of Formula Id,

Bk C

N =N-Y1 s R2 R and R are as defined above and Y, is OCONHR or OCONR R wherein R and R are as defined above, with the proviso that when R of Formula Ib is hydrogen, the amino function of the compound of Formula Ib is protected by a protecting wherein Patented Nov. 6, 1973 R and R are as defined above and Z is a leaving group,

with a compound of Formula IX,

C=N-C=N CHaS wherein M is a cation to produce a compound of Formula Ie,

wherein R and R are as defined above.

The protecting group for use in processes (b) and (c) may, for example, be the benzyl group, which is introduced by reaction with benzyl chloride. It may be split off by catalytic hydrogenation e.g. hydrogenation over palladium.

The leaving group Z of Formula VIII in process (d) is preferably halogen, e.g. chlorine, or tosylate. In addition, the cation M of Formula IX in process ((1) is preferably an alkali metal cation e.g. potassium.

The compounds of Formula I may exist either in free base or acid addition salt forms thereof. Acid addition salt forms may be obtained from free base forms in manner known per se, and vice versa.

The compounds of Formulae II, Ia and XIV wherein W is NH;, and lb employed as starting materials in processes (a), (b) and (c) respectively may be employed either in free base or preferably acid addition salt form, e.g. the hydrohalides such as the hydrochloride.

The compounds of Formula Ia are generally unstable in free base form and are thus conveniently stored in the stable acid addition salt form. For use as an intermediate in the production of other final compounds, the compounds of Formula Ia may either be reacted in acid addition salt form, or the free base form may be produced in situ by reacting the acid addition salt form with base.

The production of a compound of Formula I in accordance with the above processes may be effected as follows:

In accordance with process (a), the compound of Formula II is dissolved in a suitable solvent, e.g. chloroform and the compound of Formula III, i.e. chlorocyane, is preferably passed therethrough. The reaction is conveniently effected at a temperature of between room temperature and the boiling point temperature of the reaction mixture, preferably between 40 and 50 C. It is preferred that the reaction mixture contain a catalytic amount of an alcohol e.g. ethanol. The reaction period may be of the order of several hours. At the end of the reaction, any excess compound of Formula III is removed. The re- .action is effected in an inert atmosphere, such as nitrogen, in which case excess compound of Formula III may be removed by bubbling the nitrogen through the reaction mixture. Working up is effected in manner known per se.

In accordance with process (b), when W of Formula XIV is NH the compound of Formula la is dissolved in a suitable solvent e.g. water, with the compound of Formula XIV, preferably in the presence of an acid binding agent or buffer agent e.g. an alkali metal acetate. The reaction is conveniently effected at an elevated temperature preferably between 30 and 70 C. over a period of up to several hours. Working up is effected in manner known per se.

In accordance with process (b), when W of Formula XIV is fluorine, chlorine or bromine, the compound of Formula Ia is dissolved in a suitable solvent, preferably anhydrous e.g. anhydrous acetonitrile. The compound of Formula Ia is preferably reacted in free base form by conversion in situ from the acid addition salt form e.g. by addition of one equivalent of base such as sodium carbonate. The reaction is preferably effected in the presence of an acid acceptor e.g. triethylamine and at an elevated temperature e.g. between 30 and 70 C. for a period of several hours e.g. 2 to 3 hours. Working up is effected in manner known per se.

In accordance with process (c), when W of Formula XIV is isocyanate, a suitable solvent, preferably anhydrous e.g. anhydrous acetonitrile, is employed. A catalyst e.g. triethylamine is preferably employed. The reaction is conveniently effected at a temperature of between room temperature and the reflux temperature of the reaction mixture, preferably at reflux temperature, for a period of several hours e.g. 3 hours.

In accordance with process (c), when W of Formula XIV is fluorine, chlorine or bromine, the compound of Formula Ib is conveniently reacted in the form of its alkali metal salt e.g. by adding an alkali alcoholate, preferably sodium alcoholate to the compound of Formula Ib. The starting materials are preferably dissolved in a suitable solvent, preferably anhydrous e.g. anhydrous acetone or acetonitrile. The reaction is effected at an elevated temperature e.g. 30 to 50 over a period of several hours e.g. 4 hours. Working up is carried out in manner known per se.

In accordance with process (d), the reaction is carried out in a suitable solvent e.g. alcohol. Conveniently the reaction is carried out at an elevated temperature e.g. 70 to C. over a period of up to 2 or 3 hours e.g. /2 hour. The compound of Formula IX is preferably present in excess e.g. 2 equivalents. Working up is effected in manner known per se.

The compounds of Formula II employed as starting material in process (a) are new. They may be produced, for example by solvolysis of a compound of Formula X.

wherein R and R are as defined above,

e.g. methanolysis, with a base catalyst. The resulting compound of Formula II may be employed directly without further purification as the starting material in process (a).

The compounds of Formula X may be obtained in manner known per se from compounds of Formula XI,

wherein R and R are as defined above and X is fluorine, chlorine or bromine by reaction with a thioacetate e.g. potassium thioacetate.

The compounds of Formulae Ia and lb are special cases of compounds of Formula I. The compounds of Formula Ia are produced in a manner hereinbefore described in process (a). The compounds of Formula Ib are a special case of compounds of Formula Ic and may be produced in a manner hereinbefore described in process (b) for the production of compounds of Formula -Ic.

The compounds of Formulae III, VIII, IX, XIV, and XVI are either known or insofar as they are not known, they may be produced by the known processes or in a manner analogous to the known processes.

The compounds of Formula -I may be produced and isolated in free base or acid addition salt form.

With inorganic acids e.g. hydrogen chloride, hydrogen bromide or sulphuric acid, or with organic acids e.g. acetic acid, benzoic acid, oxalic acid or tosyl sulphonic acid, the free base forms may be converted to stable acid addition salt forms in manner known per se which forms are usually water soluble and characterised by sharp melting points.

The compounds of Formula I in free base and agriculturally and veterinary acceptable acid addition salt forms have hitherto not been described in the literature. They possess an insecticidal effect.

It is to be understood that the term insect as used herein includes not only the members of the class Insecta, but also related or similar non-vertebrate animal organisms belonging to allied classes, e.g. acarids, and including mites, ticks, spiders and the like, and the term insecticide should be construed accordingly. Thus, the compounds of Formula Id are particularly effective against spider mites.

' In addition, the compounds of Formulas Ia, Ic and Id possess a fungicidal effect.

Moreover, generally, the compounds of Formula I exhibit only low toxicity in warm blooded animals.

Thus, the compounds of Formula I are useful as insecticides, and the compounds of Formulae Ia, Ic and Id are furthermore useful as fungicides.

To these ends, the compounds may be employed in combating insects and fungi in plant loci, inhabited rooms e.g. cellars, attics and stables, and for the topical treatment of animals.

-In combating insects and fungi the compounds may be applied by conventional methods and with conventional equipment e.g. by treating the plants, objects or animals to be protected with the compounds, or with compositions containing the compounds as the or one of the active agents.

Insecticidal compositions for use in combating insects comprise a compound of Formula I, in free base or agriculturally or veterinary acceptable acid addition salt form, as active agent, in association with an insecticidal carrier.

Fungicidal compositions for use in combating fungi comprise a compound of Formula Ia, Ic or Id, in free base or agriculturally or veterinary acceptable acid addition salt form, as active agent in association with a fungicidal carrier.

The compositions may be in the form of, for example, liquid sprays, spraying powders, dusting powders, granulates, strewing agents, pastes and aerosols.

The liquid sprays for plant treatment may contain the usual non-phytotoxic solvents and diluents, such as for example alcohols, glycols, glycolic ethers, aliphatic and aromatic hydrocarbons; especially xylene or alkyl naphthalenes and other petroleum distillates, and ketones, especially cyclohexanone or isophorone.

Emulsifiable liquid sprays (emulsion concentrates) may furthermore contain appropriate surface active agents, such as wetting and emulsifying agents, e.g. polyglycol ether, formed by the reaction of alkylene oxide with high molecular weight alcohols, mercaptans or alkyl phenols, and/ or alkyl benzenesulphonates.

The solid preparations (dusting, strewing and solid spraying forms) are produced in known manner 'With the usual inert mineral carrier materials, such as for example diatomaceous earth, talc, kaolinite, attapulgite, pyrophillite, artificial mineral fillers based on SiO and silicates, limestone, decahydrate, and plant carriers, such as shell flour fillers. Wettable powder forms of compositions to be suspended in water may furthermore contain appropriate wetting and dispersing agents, e.g. sodiumlauryl sulphate, sodium-dodecyl benzenesulphonate, condensation products from naphthalene sulphonate and 6 formaldehyde, polyglycol ether, lignine derivatives (e.g. sulphite liquor).

The granulates are prepared in accordance with processes known per se by coating or impregnating granular carrier materials such as pumice, limestone, attapulgite, kaolinite and plant shell material, with the compounds, or solutions or formulations thereof.

Aside from the above mentioned carrier materials and surfactants, compositions of the invention may contain special additives, such as for example stabilizing agents, deactivators (for solid preparations with carriers having an active surface), agents for the improvement of adhesiveness to, for example plants, anticorrosives, defoaming agents and pigments.

The compounds of the invention may be present in the compositions as mixtures with other known active agents. The concentrate forms of composition generally contain between 1 and preferably between 5 and 50% by weight of active agent. Application forms generally contain between 0.02 and 90%, preferably between 0.1 and 20% by weight of active agent.

The compositions may be produced in known manner, e.g.:

(a) 25 parts by weight of a compound of Formula I, in free base or acid addition salt form, are mixed with 25 parts by weight of isooctylphenyldecaglycol ether and 50 parts by weight of xylene, whereby a clear solution is obtained which may be readily emulsified in water. The concentrate is diluted with water to the desired concentration.

(b) 25 parts by weight of a compound of Formula I, in free base or acid addition salt form are mixed with 30 parts by weight of isooctylphenyloctaglycol ether and 45 parts by weight of a petroleum fraction having a boiling point of 210-280 C. (D 0.92). The concentrate is diluted with water to the desired concentration.

(c) 50 parts by weight of a compound of Formula I, in free base or acid addition salt form, are mixed with 50 parts by weight of isooctylphenyloctaglycol ether. A clear concentrate is obtained which may be readily emulsi-fied in water and which is diluted with water to the desired concentration.

The following application examples illustrate the insecticidal eifect of the compounds of the invention, but in no way limit the scope thereof. All percent concentrations are percent parts by weight.

INSECTICIDAL CONTACT EFFECT AGAINST BRUCHIDIUS OBTECTUS (BEAN WEEVIL) Petri dishes having a diameter of 7 cc. are sprayed by means of a spraying nozzle with 0.1 to 0.2 cc. of an emulsion containing a compound of Formula I in acid addition salt form, made up in accordance with composition Example (a). After drying the coating for about 4 hours, 10 Bruchidius imagos are placed in each dish which is covered with a lid of fine mesh brass wire gauze. The insectsare kept without food at room temperature. After 2 days the rate of mortality is determined. The mortality is indicated as a percentage. means that all the bean weevils were killed, 0% means that no bean Weevil was killed.

INS'ECTICIDAL CONTACT EFFECT AGAINST APHIS FABAE (BLACK BEAN WEEVIL) Broad bean plants (Vicia faba) are sprayed to run off with a spraying liquor which contains a compound of Percent Active agent Rate of Active agent concentration mortality Z-Imino-B-dimethylamino-l,3-dithiane-bishydrochloride 0. 0125 100 2-methylcarbamoyloximino-E-dimethylamino-1,3dithiane 0.05 100 INSECTICIDAL CONTACT EFFECT AGAINST EPHEST IA KUEHNIELLA (FLOUR MOTH) Petri dishes having a diameter of 7 cm., each containing 10 caterpillars having a length of 10 to 12 mm., are sprayed by means of a spraying nozzle with 0.1 to 0.2 cc. of an emulsion containing a compound of Formula I, in free base or acid addition salt form, made up in accordance with composition Example (a). The dishes are then covered with a lid of fine mesh brass gauze. After drying the covering a wafer is given as food and renewed as required. After five days the rate of mortality is determined as a percentage by counting the live and dead insects. 100% means that all caterpillars were killed, means that no caterpiller was killed.

INSECTICIDAL CONTACT EFFECT AGAINST T RI- BOLIUM CONF US UM (CONFUSED FLOUR BEE- TLE) Petri dishes having a diameter of 7 cm. are sprayed by means of a spraying nozzle with 0.4 cc. of an emulsion containing 0.0125 of Z-cyanimino--diamethylamino- 1,3-dithiane made up in accordance with composition Example (a). After drying the coating for about 4 hours 30 T ribolium images are placed in each dish which is covered with a lid of fine mesh brass wire gauze. The insects are kept without food at room temperature. After 72 hours the rate of mortality is determined. The mortality rate is indicated as a percentage. 100% means that all the flour beetles were killed, 0% means that no flour beetle was killed. Evaluation shows a mortality rate of 100%.

INSECTICIDAL CONTACT EFFECT AGAINST CA- LANDRA GRANARIA (GRAIN WEEVIL) Petri dishes having a diameter of 5.5 cm. are sprayed by means of a spraying nozzle with 0.4 cc. of an emulsion containing 0.0125 of 2-cyanimino-5-dimethylamino- 1,3-dithiane made up in accordance with composition Example (a). After drying the coating for about 4 hours, the 30 Calandra images are placed in each dish which is covered with a lid of fine mesh brass wire gauze. The insects are kept without food at room temperature. After 72 hours the rate of mortality is determined. The mortality rate is indicated as a percentage. 100% means that all the grain weevils were killed, 0% means that no grain weevil was killed. E aluat n shows a m rta y of l00%.

8 FUNGICIDAL EFFECT AGAINST UROMYCES PHA- SEOLI (BEAN RUST)-SYSTEMIC EFFECT Potted bean plants (Phaseolis vulgaris) are Watered in the 2-leaf stage with 70 cc. of an emulsion containing 0.05% of a compound of Formula Ia, Ic or Id, in free base or acid addition salt form, made up in accordance with composition Example (a) such that the green parts of the plants remain untouched. After 24 hours the plants are infected with spores of the bean rust (Uromyces phaseoli). They are kept for 2 days at 100% relative atmospheric humidity and subsequently for 10 days under normal laboratory conditions in artificial light, the infestation then being evaluated. For the evaluation of the results the following evaluation range is used:

l=no eifect (0-5% effect) 3=weak effect (550% effect) 6=medium to good effect 50-95 effect) 9=very good effect -100% eifect) Evaluation of the Active agent: fungicidal effect 2 imino 5- dimethylamino 1,3 dithiane-bishydrochloride 9 2-oximino-S-dimethylarnino-1,3-dithiane 9 2 carbethoximino 5 dimethylamino 1,3 dithiane-hydrogen oxalate 9 FUNGICIDAL CONTACT EFECT AGAINST UROMYCES PHASEOLI Potted bean plants in the 2-leaf stage are sprayed twice on a turntable by means of a spraying nozzle with spraving liquor containing 0.05 of a compound of Formula Ia, Ic or Id, in free base or acid addition salt form, made up in accordance with composition Example (a) (approximately 0.7 cc. per plant). The plants are covered with a thin layer of the liquor which does not run off. The layer is allowed to dry ofi. After 24 hours the plants are sprayed with a suspension of Uromyces spores. Then they are kept for 2 days at relative atmospheric humidity and subsequently for 10 days under normal laboratory conditions, infestation being then evaluated according to the evaluation range indicated in the preceding example.

Evaluation of the Active agent: fungicidal effect 2 imino-S-dimethylamino-1,3-dithiane-bis-hydrochloride 9 2-oximino-5-dimethylamino-1,3-dithiane 9 2 carbethoximino-S-dimethylamino1,3-dithianehydrogen oxalate 9 Z-methyIcarbamoyloximino 5 dimethylamino- 1,3-dithiane FUNGICIDAL EFFECT AGAINST ERYSIPHE GRAMINIS (BARLEY BLIGHT) SYSTEMIC EF- FECT Barley plants (10 plants per pot) in the Heat stage, the leaves having a length of 6 to 8 cm., are sprayed with spraying liquor containing 0.05 of a compound of Formula Ia, 10 or Id, in free base or acid addition salt form, made up in accordance with composition Example (a) such that the green parts of the plants remain untouched. After about 24 hours the plants are dusted with conidia of blight. Subsequently the plants are kept for 7 days at 60-80% relative atmospheric humidity and in constant light conditions. The fungicidal effect is determined according to the evaluation range indicated in the two preceding examples.

Evaluation of the Active agent: fungicidal effect 2 imino-5-dimethylamino1,3-dithiane-bis-hydro- Z-carbethoximino-5-dimethylamino-1,3-dithiane 9 FUNGICIDAL CONTACT AGAINST ERYSIPHE GRAMINIS Barly plants (10 plants per pot) in the l-leaf stage, the leaves having a length of 6-8 cm., are sprayed all over on a turntable nearly to run oif with a spraying liquor containing 0.05% of Z-methylcarbamoyl-oximino-S-dimethylamino-l,3-dithiane made up in accordance with composition Example (a), by means by a spraying nozzle. The plants are thus covered with a thin layer of the liquor which does not run off. The liquor is allowed to dry olf and the plants are dusted with conidia of blight after about 4 hours. Subsequently the plants are kept for 7 days at 60-80% relative atmospheric humidity and in constant light conditions. Then the fungicidal effect is determined according to the evaluation range indicated in the preceding example. A result of 9 was obtained.

ACARICIDAL CONTACT EFFECT AGAINST TET RANYCH US T ELARIUS (SPIDER MITE) Bean plants (Phaseolus vulgaris) are sprayed to run off with an emulsion containing 0.05% of Z-methylcarbamoyloximino-S-dimethylamino-l,B-dithiane made up in accordance with composition Example (a). These bean plants are strongly infected with all stages of development of the spider mite. After 2 days the rate of mortality is determined as a percentage by counting the live and dead mites. 100% means that all the spider mites are killed, means that no spider mite was killed. Evaluation shows a mortality rate of 100% The following examples illustrate the production of the compounds of general Formula I, but in no way limit the scope of the invention. The temperatures are indicated in' degree centigrade.

Example 1.-2-imino-S-dirnethylamino-1,3-dithiane-bishydrochloride (process a) In this example the reaction is effected in an atmosphere of nitrogen:

47 g. (0.2 mol) of 1,3-bis-acetylthio-2-dimethyl-aminopropane are added to a solution of 0.8 g. of sodium metal in 800 cc. of absolute methanol and the mixture is subsequently boiled under reflux for 4 hours. The methanol is completely distilled off and the remaining residue is dissolved in 1000 cc. of chloroform, is cooled to 0-l0, and hydrogen chloride is passed through until an excess of at least 0.2 mol of hydrochloric acid is dissolved in chloroform. 6 cc. of ethanol are added. Chlorocyane is passed through the chloroform solution at 40-50 during the course of about 5 hours while stirring vigorously and the mixture is then stirred for a further hour at 4050. After cooling the main part of the excess chlorocyane is removed by blowing nitrogen through the solution and the precipitated salt which is washed with methanol is collected. After drying in a high vacuum at 50 colourless crystals are obtained which may be recrystallized from methanol, M.P. 243-45".

Analysis.-C H N S .2HCl; molecular weight: 249. Calc. (percent): C, 28.9; H, 5.6; N, 11.2; S, 25.7; C1, 28.5. Found (percent): C, 29.4; H, 5.5; N, 11.4; S, 26.1; C1, 28.5. I

Example 2.-2-oximino-5-dimethylamino-1,3-dithiane (process b) 21 g. (0.084 mol) of 2-imino-5-dimethylamino-1,3-dithiane-bis hydrochloride, 6.5 g. of hydroxylamine hydrochloride and 7.6 g. (0.093 mol) of sodium acetate dissolved together in 150 cc. of water and heated to 65 during the course of one hour while stirring. The solution is heated to 75 for a further 15 minutes and is cooled. After adding 8.9 g. of soda the reaction solution is extracted four times with 70 cc. amounts of ether. The ether is removed by evaporation and the remaining residue is recrystallized from methanol. Colourless crystals, having a M.P. of 203, are obtained.

Analysis.C H N OS molecular weight: 192.Calc. (percent): C, 37.7; H, 6.2; N, 14.6; S, 33.4. Found (percent): C, 37.6;H, 6.3; N, 14.6; S, 33.8.

Example 3.-2-isopropylimino-S-dimethylamino-1,3-dithiane-bis-hydrogen oxalate (process b) 5 g. (0.02 mol) of 2-imino-5-dimethylamino-1,3 dithiane-bis-hydrochloride in 50 cc. of water are heated to 40. 5 g. (0.068 mol) of isopropylamine in 15 cc. of water are added dropwise during the course of 30 minutes. The mixture is subsequently stirred at 40 for 2 hours. The mixture is then extracted thrice with cc. amounts of chloroform, the combined extracts are washed with water, dried over sodium sulphate, and the chloroform is evap orated. The residue is taken up in 30 cc. of absolute ether, a solution of a small amount of excess oxalic acid in ether is added, and the precipitated salt is recrystallized from methanol/ether. The bis-hydrogen oxalate is obtained in the form of colourless crystals, having a M.P. of

Analysis.-C H N S .2C H O molecular weight: 398.Calc. (percent): C, 39.2; H, 5.5; N, 7.0. Found (percent): C, 38.8; H,'5.6; N, 7.3.

Example 4.-2-carbethoximino-S-dimethylamino-1,3-dithane (process b) 10 g. (0.04 mol) of 2-imino-5-dimethylamino-1,3-dithiane-bis-hydrochloride are stirred with 4.2 g. (0.04 mol) of sodium carbonate in 200 cc. of absolute acetonitrile, 10 g. of chloroformic acid ethyl ester are added dropwise at room temperature to the slurry, the temperature is allowed to rise to 60 after stirring for 1 hour, and the mixture is kept at 60 for 2 hours. After cooling 10 g. of triethylamine are added and the precipitated salt is filtered off. The solvent is evaporated and the residue is taken up in chloro form, is washed with water and the chloroform is dried with sodium sulphate. After evaporation of the chloroform volatile impurities are removed in a high vacuum. The compound is obtained in the form of an oil.

Analysis.C H N O S molecular Weight: 248.- Calc. (percent): C, 43.5; H, 6.4; N, 11.3; S, 25.8. Found (percent): C, 43.8; H, 7.0; N, 11.2; S, 25.3.

Example 5.--Hydrogen oxalate of the Z-carbet-hoximino-S- dimethylamino-l,3-dithiane The compound is obtained by the addition of a corresponding amount of an etheral solution of oxalic acid to the solution of the base. The precipitated hydrogen oxalate is recrystallized from alcohol in the form of colourless crystals and has a M.P. of 124-126.

Analysis..C H N O S .C H O molecular weight: 338.Calc. (percent): C, 39.1; H, 5.9; N, 8.3; S, 18.9. Found (percent): C, 39.2; H, 6.0; N, 8.3; S, 18.8.

Example 6.2-acetylimino-S-dimethylamino-1,3-dithiane (process b) 4.5 g. (0.05 mol) of acetyl chloride in 50 cc. of absolute acetonitrile are added dropwise and while stirring to 7.5

g. (0.03 mol) of 2-imino-5-dimethylamino-1,3-dithianebis-hydrochloride dissolved in 100 cc. of absolute acetonitrile. 12.2 g. (0.12 mol) of triethylamine in 50 cc. of absolute acetonitrile are then added dropwise during the course of 1 hour. The mixture is subsequently boiled under reflux for a further 2 hours while stirring. After cooling the mixture is filtered off by suction and the filtrate is evaporated at 50 in a vacuum. The residue is taken up in 300 cc. of absolute chloroform, is washed twice with 50 cc. amounts of water, is dried over sodium sulphate, and the solvent is evaporated. A colourless oil is obtained.

Analysis..-C H N OS molecular weight: 218.Calc. (percent): C, 45.1; H, 6.4; .S, 29.2. Found (percent): C, 45.0; H, 6.7; S, 28.6.

Example 7.-2-methylcarbamoyloximino-5-dimethylamino-1,3-dithiane (process c) /NC =No-coNHcH. on, S

2 g. (0.0105 mol) of 2-oximino-S-dimethylamino-l,3-dithiane are dissolved together with 0.1 cc. of triethylamine in 50 cc. of absolute acetonitrile. 3 cc. of methylisocyanate in 30 cc. of absolute acetonitrile are added dropwise to this solution at room temperature and while stirring. The mixture is then boiled at room temperature for 1 hour and subsequently under reflux for 2 hours. The mixture is then concentrated by evaporation in a vacuum, the residue is taken up in chloroform and is Washed with water. The chloroform is dried over sodium sulphate and removed by evaporation and the residue is recrystallized from strongly boiling petroleum ether with a small amount of ethanol. Colourless crystals, having a M.P. of 118120, are obtained.

Analysis.-C H N O S molecular weight: 249.- Calc. (percent): C, 38.9; H, 6.3; N, 16.9; S, 25.7. Found (percent): C, 38.7; H, 6.3; N, 16.9; S, 26.1.

Example 8.2- (N,N-dimethyl-carbamoyloximino) --dimethylamino-1,3-dithiane (process c) 3.8 g. (0.02 mol) of 2-oximino-5-dimethylamino-1,3-dithiane in 50 cc. of absolute ethanol are added to a solution of 0.5 g. (0.021 mol) of metallic sodium in 100 cc. of absolute ethanol. When a clear solution is obtained the solvent is removed by evaporation and the residue is taken up in 150 cc. of absolute acetone. A solution of 2.6 g. (0.024 mol) of dimethylcarbamoyl chloride in 100 cc. of absolute acetone is added dropwise to this solution while stirring, the mixture is stirred at 40 for a further 4 hours, is cooled and a further 1.5 g. of triethylamine are added. The mixture is stirred for a further minutes, the precipitate is filtered off by suction, the filtrate is concentrated by evaporation at 40 in a vacuum, the residue is dissolved in 300 cc. of chloroform, is washed twice with 50 cc. amounts of Water, is dried over sodium sulphate and the solvent is evaporated. A practically colourless oil is obtained.

Analysis.C H -;N O S molecular weight: 263. Calc. (percent): C, 41.0; H, 6.5; N, 15.9; S, 24.3. Found (percent): C, 41.0; H, 6.5; N, 15.1; S, 23.6.

Example 9.-2-cyanimino-5-dimethylamino-1,3- dithiane (process d) 214 g. (1.26 mol) of potassium cyanimino-thiomethylthiolocarbonate in 600 cc. of alcohol are heated to 70- 75. A solution of 0.635 mol of 1,3-dichloro-2-dimethylamino propane (produced from 122 g. (0.635 mol) of 1,3-dichloro-2-dimethylamino-propane hydrochloride in 400 cc. of alcohol by adding 35.2 g. (0.63 mol) of KOH in 200 cc. of alcohol after filtering off the precipitated KCl) is added dropwise and while stirring to thissolution at -75 during the course of 20 minutes. The mixture is stirred at the same temperature for a further 10 minutes and is cooled to room temperature. The precipitated potassium chloride is filtered oil? and the filtrate is concentrated by evaporation at 50 in a water jet vacuum. The oily residue is taken up in 500 cc. of chloroform and is washed twice with 200 cc. amounts of water and is dried with sodium sulphate. The solvent is evaporated at 50 in a vacuum and 50 cc. of ether are added to the oily residue and the mixture is cooled to 0". Thus the Z-cyanimino-S- dimethylamino-1,3-dithiane crystallizes. This compound is filtered ofi by suction, is washed with a small amount of ether or alcohol and the pure compound with a M.P. of 98.5 is obtained.

Analysis.C-;H N S molecular weight: 201.3. Calc. (percent): C, 41.8; H, 5.5; N, 20.9; S, 31.9. Found (percent): C, 41.5; H, 5.6; N, 21.0; S, 32.2.

Example 10.--Hydrogen oxalate of the Z-cyanimino-S- dimethyl amino- 1, 3-dithiane 50 g. (0.25 mol) of 2-cyanimino-S-dimethylamino-1,3- dithiane are dissolved in 200 cc. of alcohol at 50 while stirring and 22.5 g. (0.25 mol) of oxalic acid in cc. of alcohol are added. The hydrogen oxalate precipitates at once. After cooling to room temperature it is filtered off by suction. A further amount of hydrogen oxalate precipitates while concentrating the mother liquor to about 50 cc. After drying at 5 0 in a vacuum the hydrogen oxalate of the Z-cyanimino-5-dimethylamino-1,3-dithiane has a M.P. of 154'.

Analysis. C H N S .C H O molecular weight: 291.34.Calc. (percent): C, 37.1; H, 4.5; N, 14.4; S, 22.0. Found (percent): C, 37.0; H, 4.8; N, 14.8; S, 22.4.

Example 11.2-imino-S-isopropylamino-1,3-dithiane (process a) This compound is produced by a process analogous to that described in Example 1.

Example 12.2-cyclohexylimino-5-diethylamino-1,3- dithiane (process b) This compound is produced by a process analogous to that described in Example 3.

Example 13.2-cyclopentylimino-S-dimethylamino-1,3- dithiane (process b) This compound is produced by a process analogous to that described in Example 3.

Example 14. 2-carbo-tert.butoximino-5-n-pentylamino- 1,3-dithiane (process b) This compound is produced by a process analogous to that described in Example 4. However, the monoalkylsubstituted amine function of the 2-imino-5-n-pentylamino- 1,3-dithiane-bis-hydrochloride is protected by reaction with benzyl chloride to obtain the benzyl substituted amine derivative. The benzyl substitutent is removed from the final compound by hydrogenation over a palladium catalyst.

Example 15.2-carbo-cyclopentoximino-S-dimethylamino-1,3-dithiane (process b) This compound is produced by a process analogous to that described in Example 4.

Example 16.--2-carbo-cyclohexyloximino-S-diethylamino-1,3-dithiane (process b) This compound is produced by a process analogous to that described in Example 4.

Example 17.-2-carbo-p-chloroethoximino-S-di-n-propylamino-1,3-dithiane This compound is produced by a process analogous to that described in Example 4.

Example 18.-2-carbo-[4-chlorocyclohexyl]oximino- S-dimethylamino-1,3-dithiane (process b) This compound is produced by a process analogous to that described in Example 4.

Example l9.--2-p-fluoro-phenylcarbamoyloximino-5- dimethylamino-1,3-dithiane (process c) This compound is produced by a process analogous to that described in Example 7.

Example 20.2-p-methyl-phenylcarbamoyloximino-S- dimethylamino-l,3-dithiane (process c) This compound is produced by a process analogous to that described in Example 7.

Example 21.2-naphthyl-carbamoyloximino-S-dimethylamino-1,3-dithiane (process c) This compound is produced by a process analogous to that described in Example 7.

Example 22.2-(N-methyl-N-phenyl-carbamoyloximino)--dimethylamino-1,3-dithiane (process c) This compound is produced by a process analogous to that described in Example 8.

What is claimed is:

1. A compound of the formula:

R1\ S C s 2 R is alkyl of 1 to 5 carbon atoms,

R is hydrogen or alkyl of 1 to 5 carbon atoms and Y is hydrogen, hydroxy, alkyl of 1 to 5 carbon atoms, cycloalkyl of 5 or 6 carbon atoms, cyano, -COOR --COR wherein R is alkyl of 1 to 5 carbon atoms, alkenyl of 2 to 5 carbon atoms, cycloalkyl of 5 or 6 carbon atoms, or fluoro, chloro or bromo substituted alkyl of 1 to 5 carbon atoms, alkenyl of 2 to 5 carbon atoms or cycloalkyl of 5 or 6 carbon atoms, -OCONHR or --OCON R R wherein R is alkyl of 1 to 5 carbon atoms, ph'enyl, naphthyl phenyl or naphthyl substituted by alkyl of 1 to 5 carbon atoms, fluorine, chlorine or bromine and R is hydrogen or alkyl of 1 to 5 carbon atoms,

wherein in free base or agriculturally or veterinary acceptable acid addition salt form.

2. A compound of the Formula I,

wherein R is alkyl of 1 to 5 carbon atoms,

R is hydrogen or alkyl of 1 to 5 carbon atoms and Y is hydrogen, hydroxy, alkyl of 1 to 5 carbon atoms, cycloalkyl of 5 or 6 carbon atoms, --COOR C'OR wherein R is alkyl of 1 to 5 carbon atoms, alkenyl of 2 to 5 carbon atoms, cycloalkyl of 5 or 6 carbon atoms, or fluoro, chloro or bromo substituted alkyl of l to 5 carbon atoms, alkenyl of 2 to 5 carbon atoms or cycloalkyl of 5 or 6 carbon atoms, -OCONHR or wherein R is alkyl of 1 to 5 carbon atoms, phenyl, naphthyl phenyl or naphthyl substituted by alkyl of l to 5 carbon atoms, fluorine, chlorine or bromine and R is hydrogen or alkyl of 1 to 5 carbon atoms,

in free base or agriculturally or veterinary acceptable acid addition salt form.

3. The compound of claim 1 which is Z-imino-S-dimethy1amino-l,3-dithiane.

4. The compound of claim 3 in the form of the bishydrochloride.

5. The compound of claim 1 which is isopropylimino- S-dimethylamino-1,3-dithiane.

6. The compound of claim 5 in the form of the bishydrogen oxalate.

7. The compound of claim 1 which is 2-carbethoximino- S-dimethylamino-1,3-dithiane.

8. The compound of claim 7 in the form of the bishydrogen oxalate.

9. The compound of claim 1 which is Z-acetylimino- S-dimethylamino-1,3-dithiane.

10. The compound of claim 1 which is 2-methylcarbamoyloximino-S-dimethylamino-1,3-dithiane.

11. The compound of claim 1 which is 2-(N,N-d'imethyl-carbamoyloximino)-5-dimethylamino-1,3-dithiane.

12. The compound of claim 1 which is Z-cyanimino- S-dimethylamino-1,3-dithiane.

13. The compound of claim 12. in the form of the bishydrogen oxalate.

References Cited UNITED STATES PATENTS 3,193,561 7/1965 Addor 260327 3,480,647 11/1969 Feinaucr 260327 3,484,455 12/ 1969 Addor 260-327 3,652,256 5/1972 DAmico 7180 OTHER REFERENCES Konishi: Agr. Biol. Chem., vol. 34, No. 6, pp. 926-934, June 1970.

Konishi: Agr. Biol. Chem., vol. 34, N0. 6, pp. 935-940, June 1970.

HENRY R. J I'LES, Primary Examiner C. M. S. JAISLE, Assistant Examiner 

